3,4-dihydro-2H-pyran → 21-Tetrahydropyranyl-11beta-hydroxy-1,4,16-pregnatriene-3,20-dione

HRID 34721Notes

Reaction equation

HRID 34721 reaction equation
[OH:1][C@H:2]1[CH2:22][C@@:21]2([CH3:23])[C@@H:13]([CH2:14][CH:15]=[C:16]2[C:17](=[O:20])[CH2:18]O)[C@H:12]2[C@H:3]1[C@:4]1([CH3:25])[C:9]([CH2:10][CH2:11]2)=[CH:8][C:7](=[O:24])[CH:6]=[CH:5]1.[O:26]1[CH:31]=[CH:30][CH2:29][CH2:28][CH2:27]1.S(C1C=CC(C)=CC=1)([O-])(=O)=O.[NH+]1C=CC=CC=1>ClCCl>[O:26]1[CH2:27][CH2:28][CH2:29][CH2:30][CH:31]1[CH2:18][C:17](=[O:20])[C:16]1[C@:21]2([CH3:23])[C@H:13]([C@H:12]3[C@H:3]([C@@H:2]([OH:1])[CH2:22]2)[C@:4]2([CH3:25])[C:9](=[CH:8][C:7](=[O:24])[CH:6]=[CH:5]2)[CH2:10][CH2:11]3)[CH2:14][CH:15]=1

Participants

5

Reactant 3

HCID 80803,4-dihydro-2H-pyranHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 14233399Deoxyprednisolone-16-ene

Product 1

HCID 2283932121-Tetrahydropyranyl-11beta-hydroxy-1,4,16-pregnatriene-3,20-dioneYield 80.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 11β,21-dihydroxy-1,4,16-pregnatriene-3,20-dione (200 mg, 0.58 mmole) in dichloromethane (40 ml) were added 2,3-dihydropyran (0.2 ml, 2.19 mmole) and anhydrous pyridinium tosylate (70 mg, 0.32 mmole). After stirring for 4 hours at room temperature, the reaction mixture was washed with water (100 ml) and evaporated to give a yellowish oil. This oil was placed on silica gel column and eluted with benzene ethyl acetate (2:1). Evaporating the solvent afforded pure white foam of 21-tetrahydropyranyl-11β-hydroxy-1,4,16-pregnatriene-3,20-dione (191 mg. 77.1%), 1H--NMR (CDCl3) δ 1.25 (s, 3H, 13--CH3), 1.49 (s, 3H, 10--CH3), 4.63-4.38 (m, 3H, 20--CH2 -- and 11--H), 4.68 (t, 1H, J=5 Hz, --O--CH--O--), 3.5, 3.85, 1.1 (m. pyranyl H), 6.01 (s, 1H, 4--H), 6.27(dd, 1H, J=10 and 2 Hz, 2--H), 6.73(m, 1H, 16--H), 7.31(d, 1H, J=10 Hz, 1--H).

Workup

  1. washthe reaction mixture was washed with water (100 ml)
  2. customevaporated
  3. customto give a yellowish oil
  4. washeluted with benzene ethyl acetate (2:1)
  5. customEvaporating the solvent

Sources & evidence

ORD record
ord-1b69a51d454348939819e1e9192c240a
Source dataset
uspto-grants-1988_08
Patent number
US04762919

Reaction notes

Loading…